A new method for the synthesis of poly(dichlorophosphazene)
at ambient temperatures is
described. It involves the initiation of
Cl3PNSiMe3 with small amounts of
PCl5 in CH2Cl2 to yield
poly(dichlorophosphazene), (NPCl2)
n
, with
narrow polydispersities. The molecular weight of
poly(dichlorophosphazene) was controlled by altering the ratio of monomer to
initiator. The polymer chains were
found to be active after chain propagation since further addition of
monomer resulted in the formation
of higher molecular weight polymer. Integration of 1H
and 31P NMR spectra of these reactions
revealed
that the polymerization follows first-order reaction kinetics with
respect to monomer concentration. Active
polymer chains may be quenched or end-capped by the addition of trace
quantities of Me2(CF3CH2O)PNSiMe3 or
(CF3CH2O)3PNSiMe3.
Furthermore, PBr5, SbCl5, and
Ph3C[PF6] were also found
to be effective initiators in CH2Cl2 at
room temperature.
In infants with acute moderate-to-severe bronchiolitis who were treated in the emergency department, a single dose of 1 mg of oral dexamethasone per kilogram did not significantly alter the rate of hospital admission, the respiratory status after 4 hours of observation, or later outcomes. (ClinicalTrials.gov number, NCT00119002 [ClinicalTrials.gov].).
A new, ambient-temperature method for the direct synthesis of organo-substituted polyphosphazenes is described. It involves the initiation of a series of organophosphoranimines R(R′)-with catalytic amounts of PCl5 in CH2Cl2 to yield (after treatment with NaOCH2CF3 in the case of 3) the corresponding polyphosphazene species (NdPRR′)n (4, R ) Ph, R′ ) OCH2CF3; 6, R) with narrow polydispersities. The molecular weights of the polyphosphazenes were controlled by altering the ratio of monomer to initiator. The polymer chains were found to be active after chain propagation since further addition of monomer resulted in the formation of higher molecular weight polymer. For monomers 7 and 9 optimum polymerization behavior was found to occur at 35 °C in the absence of solvent in the presence of catalytic quantities of PCl5. These reactions proceeded to 100% completion, while maintaining molecular weight control and narrow polydispersites. In the case of polymers 4, 8, and 10, which were synthesized with a 10:1 monomer to initiator ratio in CH2Cl2, the resultant polymers were analyzed by gel permeation chromatography (GPC) (4, Mn ) 2.9 × 10 3 , polydispersity (PDI ) Mw/Mn) ) 1.07); 8, Mn ) 2.2 × 10 3 , PDI ) 1.31; 10, Mn ) 7.8 × 10 3 , PDI ) 1.23). Poly(diphenylphosphazene), ( NdPPh2)n ( 6), was insoluble in common organic solvents and was characterized by magic angle spinning (MAS) solid state 31 P NMR spectroscopy. The effects of side group steric bulk, electron-withdrawing or -donating properties, and leaving group types on the ambient-temperature cationic induced polymerizations are discussed.
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